Coloring matter of the anthracene series



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Patented Dec. 30, 1930 Ivan GUBVELMANNYAND non'n'nrr, eoonmofi; 0FsoUrH'MILwAoKEE, Am) wrrrrliir I pErrwY En, or r/rrLwAU En, wrsoonsrnnssrenons T0 THENEWPQRT oo vrPAN'Y, or CABROLLVILLE, wrsoonsm noonrormrro v on DELAWARE ooLoRInG irn'rmnnor THE nNrrrnAeEitE SERIESApplication filed December This invention relates 'tothe manufacture ofcoloring, matters of the anthracene series andimore particularlyto thoseintheanthra-Y quinone benzacridone series. I r v H 7 his 'a' well knownfact that anthraquinone 1:2 benza'cridones may be made by the con withthe formation of an :imid, having the 7 oo t I, .6

general type formula: 7

}NHR T' wherein It represents I an anthraquinone' body. We havet furtherfound that these acridones when made,-.as for instance from chloride y ameta-chloroor bromo-aniline body, are particularly suitable for makingvaluable vat dyestuffs bygconversion' into imids of the general typeformula given abovev and subsequent heating. of the irnids with metalThe constitution of thesefinal' products is not known to us; vIt hasbeen suggested in the literature (see German Patent 258,808)

that reactions of thistype result in .com-:

pounds having both anacridone and anacri-v dine ring, It this theory iscorrect, the formula'of our. finalproduca'or at, least; one of thetheoretically possible isomers, should be,

11, 1926. Serial no; 154,304.

However it is also'possible that the reaction results i'n the formationof a carbazole ring product would probably be as follows: i

- I foo 'These'vat poloring matters are, 'ingeneral,

structure in which case the formulaof thedark brown powders, insolublein'wat'er, al-' coholi 'falk'alies' and; dilute *inineral acids;somewhat soluble in aniline, but readily solu ble in concentratedsulphuric acid, imparting a' b'rown colorto the solution and infal- Vkalin'e hydrosulphite, giving a violet colored vat, from which cottonis-dyed violet, changing to a brown "shade" on treatment with suitableoxidizing agents; InGerman Patent No; aprocess of condensing by' meansof concen-.

tr il d Sulfuric acid an anthraquinonacri-- donylamino anthraquinoneobtained from alpha-amino-anthraquinone and a, halogenanthraquinoneacridone, in which the halo gen is para'to'theh'eterocyclic nitrogen. Our process differs therefrom in two 2 respects,

1 v t 258,808, isdescri'bed namelyi(l)*'we' operate on an anthraquinon-I acridonyl amino anthraquinone' "obtained from alpha-amindanthraquinoneand a mono or dihalogen anthraquinone-acridone in which at leastionehalogen atom is'in meta position to thehete'rocyclic nitrogen and ('2)we use aluminum chloride as thecondensing agent; The products producedby our method differ considerably in tinctorial value from the productsof said Germanpatent. If the amount of; dyestuflsrequired to produce adyeing of a given strength on the same weight of cotton cloth be takenas a criterion, the dyestuiis produced by our method are 2 to 3 times asstrong as the dyestufis of said German patent. VVhile some'variation intinctorial "strength should have beenexpected due to the use ofdifferent starting mater als,- itwas'not to be foreseen that thedifference would be manifold and in favorof th new, dyestutls; i Withoutlimiting our invention many ticular procedure, the "following" examples,in which parts by weight aregiven i-llustrate the application ofourinven tion in the pre erred form: r J g i EmampZel I I 31 7 parts-of-1-c'hloro anthr'aquin-one-2- carboxylic acidiare dissolved in amixtureo'f 200 parts of water audio parts of sodium carbonate. 43.4parts of sodium carbonateare further added together with 10.2 parts of3:4 dichloro-aniline and 1.6 parts of basic copper acetate. I The massis heated to 103 C.

V and held at this temperature under reflux, with agitation, for 4hours.The mass is then cooled to 25 (1, filtered and the filter cakeintroduced into 15O'.p'arts of 3% hydr-' chloric acid. The-whole isheated to boiling and additional, hydrochloric acid added, if necessary,to make the mixture distinctly acid. The precipitate formed is filteredand washed free ofinorganicv salts with cold Water and dried. This; dryproduct is introduccd into 120 parts of nitro-benzene and 9 parts ofacetyl chloride added.. The mixture is heated ,to 11 0120 C. and-held atthis temperature,.-for --2=hours. f-The whole is then ift cooled to2 0'G., filteredatthis'temperature and' gt he filter cakewashed with lO O,;parts I of .lalcohol. -dichloro acridone namely chloro substitutedanthraquinone 1:2 benzacridone is thus-obtained. Y

,parts of this body are introduced 100 parts of nitro-benzene, and '6parts of alpho-aminoanthraquinone, lO-partsof fine- [ly ground sodiumcarbonate and-3 parts- 01 basiccopperacetate 'are'ad ded. -The;miture isheated to 2-10" C. andqrefluxed with agitat on at'this temperature for 5hours, The

;, mass is then introduced-into 300 apart-slot water and steampassedinto; themi rture -nintil all thenitro-benzene has been removed.

The aqueous suspension obtained is then made distinctly-acid withhydrochloric aeid withhot water until {free ofinorganic salts,

' dried and finely ground.

:parts of this finely ground product-are furthenground together with;;;parts -ofg-an hydrousralulninum chloride, Themixture is heated @1353G,,- and keptat-this temperature'for zhours. The reactionmassiscooled,ground and introducedinto-QOO parts of 5 hydroehloric-aeid.Thesuspensionisboiled tor; -ininutes, filtered hot and the filter-cakemeta-chloro-aniline.

washed with hot Wateruntil free of inorganic salts. After dryingandgrinding, the coloring matter is obtained as a'dark brown powdercontaining combined chlorine and having the characteristics mentionedabove.

Example II Inan analogous manner to that of Exam- "ipfle I, acoloringnratterm'ayfbeobtainediree "of combined chlorine "by replacingthe 3 4 (lichloro-ani'li'ne used in that example with v p Thecharacteristics are, in general, the same.

Fam ne 111 In an analogous manner to that of Example I,-a "coloringmatter .unay-be obtained which dyes cotton "a:soine-what yellower shadeby replacing the amount of aluminum c'lrl oride' pecified in Example Iwith 30 parts of anhydrous zinc-chloride and?) parts of water, andincreasing *the temperature from 135 C$to 160l'-C.. l he coloring matterso obtained con-tains "combined chlorine Land is similar in propertiesto the coloring matter obtaine'd' by Ex'ample :I, but-dyes bottom a thanas 1. The{process-ofpreparing'coloring matters oftliea'rltlirac'eneseries,'whichcornprises condensing "an *anthr'aquinone'halogen substituted benzacridone whijch c'ont'ains a'halogen atom inmeta j position to --tlie imi'nolgroup in the ben'ze-ne' ringfwith anamino anthraquinone bodyand heating the resulting p'roduct=withametttlchl'orid 2. Thei-proces's "of preparing coloring mattersoftheanthraceneseriea whi'ch comprises condensing-an anthraquinone halogensubstituted benZacndone-whmh contains a halo. gen a'tom in metaposi'tion' tothe imi'no group infthe' benzene ring,'fwithza'n-aniinoanthraquin'one 'bodyand heatingthe resulting prod not with aluminumvchloride.

3. The process of preparing coloring matters of the anthracene series,which comprises condensing a chl'oro-acridone, made from 1 chloroantlrraqu inone-Q carboxylic acid and a meta-chl'oro-aniline body, withan alpha amino anthraquinone body and heat- 4. The processoipreparingcoloring mat ters of the ant-hracene series, which comprisescondenslng a chloro acr1done, made from ing the resulting product"with ametal chlo- 1 chloro anthraquinone 2 carboxylic acid and a metachloro-aniline body, with an alpha-amino-anthraquinone body and heatingthe resulting product with aluminum chloride.

5. The process of preparing coloring matters of the anthracene series,which comprises condensing a dichloro acridone, made from 1. chloro-'anthraquinone- 2 carboxylic acid and 3 4 dichloro aniline, with analphaamino-anthraquinone body and heating the resulting-product with ametal chloride.

6. The process of preparing coloring matters of the anthracene series,which comprises condensing a chloro acridone, made from 1 chloroanthraquinone 2 carboxylic and a meta-chloro-aniline, withalpha-aminoanthraquinone and heating the resulting product with a metalchloride.

7. As new articles of manufacture, the

coloring matters of the anthracene series,

which may be obtained by the process described in claim 1 and whichcoloring matters are, in general, dark brown powders insoluble in Water,alcohol, alkalies and dilute mineral acids, somewhat soluble in aniline,but readily soluble in concentrated sulfuric acid forming a browncolored solution and giving with alkaline hydrosulphite a Violet'coloredVat from which cotton is dyed Violet, changing to a brown shade ontreatment with suitable,

oxidizing agents. 1

8., As new articles 1 of manufacture, the

coloring matters of the anthracene series, which may. be obtained froma. di-chloro-' acridone, made from l-chloro-anthraquinone- .Z-carboxylicacid anda 3 4 dichloro-aniline body, by condensing thedichloro-acridone' further with an alpho-amino-anthraquinone body andheating the resulting product with a metal chloride, which coloringmatters are, in general, dark brown powders containing combinedchlorine, insoluble in water, alcohol, alkalies and dilute mineralacids, somewhat soluble in aniline, but readily soluble in concentratedsulphuric acid, forming a brown colored solution and giving withalkaline hydrosulphite aviolet colored vat from which cotton is dyedViolet changing to a brown shade on treatment with suitable oxidizingagents.

In testimony whereof we have hereunto subscribed our 7 1 names.

.IVAN GUBELMANN.

ROBERT J. GOODRICH. WILLIAM DETTWYLER.

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